Method of killing insects with mono-and di-thiophosphoric acid esters



United States Patent O 3,178,337 METHOD OF KILLING INSECTS WITH hION AND DI-TIIIOPHOSPHORIC ACE ES'I'ERS Karl Lutz, Basel, and Max Schuler, Arlesheim, Switzerland, assignors to Sandoz Ltd. (also known as Sandoz AG.) Basel, Switzerland No Drawing. Original application July 14, 1960, Ser. No. 42,751. Divided and this application Sept. 28,

1964, Ser. No. 405,641

14 Claims. 01. 167-22) This is a division of application Serial No. 42,751, filed July 14, 1960.

The present invention is concerned with new insecticidal and acari idal monothiophosphoric and dithiophosphoric acid esters. The invention is also concerned with the use of the said esters and/or compositions containing the same, for combating pests, more especially insects and spider mites.

The aforesaid new monothiophosphoric and dithiophosphoric acid esters correspond to the formula R10 Y R4 R3 i sbrr-ii-ri-ono Rao (1) wherein each of R and R represents CH or C H R stands for methyl, ethyl or propyl, R stands for H, methyl, ethyl or propyl, and Y stands for an oxygen atom or a sulfur atom.

Compounds I can advantageously be prepared by reacting a compound of the formula R4 IO 1'13 X(ilH( JNCHO (II) wherein R and R have the precedingly-recited significances and X stands for halogen with a compound of the formula wherein Y is as precedingly recited and Z is a cation. Where Z is H, the reaction is carried out in the presence of an acid-binding agent.

The reaction is advantageously carried out in a solvent such as acetone, methylethylketone, dioxane or Water or in an aliphatic or aromatic hydrocarbon or in a mixture of such solvents, at normal or slightly raised temperature.

Suitable compounds of Formula II are for example the chloroacetyl-N-alkyl-formamides such as chloroacetyl-N- methyl-formamide, chloroacetyl N ethyl formamide, chloroacetyl-N-isopropyl-formamide, as Well as u-chloro propionyl-N-methyl-formamide; also the corresponding brorno-compounds. These intermediates are themselves new compounds.

Suitable compounds of formula III are for example:

The monothiophosphoric and dithiophosphorie acid esters I of the present invention are liquid at room temperature (about 20 to about 30 C.). They are generally soluble in oils as well as in organic solvents, and

ice

are easily emulsifiable in Water. The new esters I are outstandingly suitable for combating pests, more especially insects and spider mides (Tetranychidae sp.), in the protection of plants. Some of the compounds I are distinguished by excellent systemic action.

As will hereinafter appear, the new compounds I are distinguished from known systemically acting insecticides by reduced toxicity to warm-blooded animals, while having as good or better systemic action.

1. ORAL TOXICITY OF ACTIVE SUBSTANCES LDa s-1kg.) No. Formula of active ingredient of composition White Rat mouse (Cl-IgOhPSSCHzCONHOHa. 130 (CHzO)2PSSOzH4SC2H5 (CH3O) P(O)SC2H4SO2H 40 (CH30)2P(S)OGZH4SO2H5 (technical mixture of the thiono and thiolo forms) 64 5 (CHaO)gPSSCH2CO-NCH3 210 CHO NorE.Compositions 1 to 4 are commercial preparations available on the market; composition 5 is according to Example 1 of the present application.)

2. SYSTEMIC ACTION Potted spiderwort plants are each Watered with 100 milliliters of an aqueous emulsion of the insecticide being tested in such manner that the emulsion comes in contact only with the root system of the plants.

On the next day, each plant has applied thereto 30 grasshoppers (Carausius morosus) in the 2nd larval stage. The systemic-insecticidal action of the various insecticides is checked daily by counting the number of dead insects.

The observed results are characterized by indication of the mortality (in percent of the applied insects) after x days after the treatment (percent/x):

I, the latter are advantageously admixed with emulsifying agents, for example with liquid polyglycol ethers obtained from higher alcohols, mercaptans or alkylphenols by adding on ethylene oxide, then emulsifying the mixture in water, and applying the emulsion by spraying thereof onto the surfaces to be treated. Solution aids, such as suitable organic solvents, for example monoor poly-alcohols, ketones, aromatic hydrocarbons, mineral oils, etc., may be incorporated into the mixtures of ester I and emulsifying agents. In order to produce Watersuspendible pulverulent products, there may also be incorporated into the said mixtures, solid carriers such as talc, kaolin, kieselguhr, bentonite, etc. The liquid or pulverulent products are emulsified or dispersed in water before being used, it being preferable that the resultant emulsions or dispersions should contain 0.005 to 0.2% by Weight of ester I.

However, the new monothiophosphoric and dithiophosphoric acid esters 1 can also be used without emulsifiers, in which event the esters are advantageously admixed with adhesion promoting agents and inert carriers, such as talc, kaolin, kiselguhr, bentonite, etc., or with a mixture of such carriers, so that the product may be used as a dusting composition or scattering composition.

The following examples set forth presently preferred exemplary embodiments of the invention. Parts and percentages are by weight unless otherwise indicated. The relationship or parts by weight to parts by volume is the same as that between grams and milliliters. Temperatures are in degrees centigrade.

A. Examples of the preparation of the intermediates of the formula ClCHCON-R3 The general method for the preparation of the inter-- EN G is stirred in dropwise at about 80 in the course of 1 to 2 hours. Stirring of the reaction mixture is then further continued at the said temperature until hydrogen chloride development has practically ceased.

EXAMPLE 1 59 parts (:1 mol) of the compound of the formula CH NHCHO are dissolved in 100 parts by volume of trichloroethylene and the resultant solution is stirred dropwise in the course of 1 to 2 hours into a solution, heated to 80, of 112 parts (=1 mol) of 'chloroacetic acid chloride in 200 parts by volume of trichloroethylene. Stirring is then continued for about one more hour at 80. The resultant reaction product of the formula is recovered from the reaction mixture by distillation.

Yield: 85%. Boiling point: 7071/0.4 mm. 11 1.4960. Clcalc.: 26.2%. Found: 26.5%.

EXAMPLE 2 The procedure according to Example 1 is repeated, using-as starting materials-chloroacetic acid chloride and the formamide of the formula C H NHCH0 The obtained intermediate of the formula ClCHgCON-CgH has a boiling point of 6970/0.4 mm.

Clcalc.: 23.7%. Found: 24.2%.

EXAMPLE 3 In analogous monner, from chloroacetic acid chloride and the formamide of the formula iso-C H NHCHO there is obtained the intermediate of the formula ClCHgCONC3H7lSO which has a boiling point of 6l63/0.3 mm. 1.4482. Clcalc.: 21.7%. Found 21.1%.

EXAMPLE 4:

In similar manner, from chloroacetic acid chloride and the formamide of the formula n-C H- NHCO there is obtained the intermediate of the formula ClCH CONC H n there is obtained the intermediate of the formula CH OHClOONCH;

('DHO which boils at 64-67/0.5 mm.

calc.: 23.7%. Found: 23.3%. Found: 9.46%.

B. Examples of the preparation and use of the end prodacts of the formula n =1.4812. Cl- N calc.: 9.36%.

EXAMPLE 6 68 parts of the compound of the formula GlCH GONOH and parts of the compound of the formula (CH O) PSSNH are stirred together for 4 hours in 300 parts by volume of chloroform at about 55. The chloroform layer is then washed successively with water, 5% aqueous sodium bicarbonate solution and again with water. After drying the chloroform layer and distilling oif the chloroform, there is obtained in an about 85% yield the compound of the formula (01130? s S 01120 ONCH in the form of a yellow oil. n =1.5522. Pcalc.: 12.0%. Found: 12.1%. S calc.: 24.9%. Found: 25.4%.

EXAMPLE 7 30 parts of the compound of the formula ClCH C01TT-C H and 37 parts of the compound of the formula (CH O) PSSNH are stirred together for 2 hours in parts by volume of acetone at 50. After the addition of 600 parts by volume of Water, the organic layer is extracted with chloroform, the chloroform extract washed successively with water, 5% aqueous sodium bicarbonate solution and again with water, and then dried. After distilling off the chloroform, there remains as residue in an about 85% yield the compound of the formula (CH3O)2P s S 01120 0N-02H5 in the form of a yellow oil. n =1.5384. P-calc.: 11.4%. Found: 11.6%. S-calc.: 23.6%. Found: 24.4%.

5 EXAMPLE 8 33 parts of the compound of the formula o1oH,G0N0H(CH and 37 parts of the compound of the formula (CH O) PSSNH are stirred together for 4 hours in 200 parts by volume of dioxane at 60". After the addition of 1000 parts by volume of water, the organic layer is extracted with chloroform. After drying the chloroform extract and distilling off the chloroform, there is obtained in an about 80% yield the compound of the formula (CH O);%SCH CON-CHUJHW in the form of a yellow-brown oil. n =1.5286. P-calc.: 10.9%. Found: 11.2%.

EXAMPLE 9 27 parts of the compound of the formula 01oH N- OH,

and 40 parts of the compound of the formula 0 ll 2 P-SNa are stirred together for 2 hours in 200 parts by volume of acetone at 50. The acetone solution is then cooled and separated from precipitated NaCl by filtration. The acetone is distilled from the filtrate, the residue taken up in ether, the ether solution washed with water and dried over sodium sulfate.

After distilling off the ether, there remains as residue in practically quantitative yield the compound of the formula calc.: 11.9%. Found: 11.7%.

EXAMPLE 10 41 parts of the compound of the formula 2H5O) l i-SNH4 and 50 parts of the compound of the formula CH3OHC1CON-CH3 are stirred together for 2 hours in 200 parts by volume of acetone at 50. After the addition of 1000 parts by volume of Water, the organic layer is extracted with chloro form. After drying the extract and distilling off the chloroform, there is obtained in an about 75% yield the compound of the formula H3 no inthe form ofayellowish oil. It =1.5257. Ncalc.: 4.7%. Found: 4.9%. Pcalc.: 10.4%. Found: 10.9%. Scalc.: 21.9%. Found: 21.8%.

EXAMPLE 11 In analogous manner (to that of Example 10), there is obtained from the compound of the formula II (CH30)gP-SNH4 and the compound of the formula 0115011010 ON-CHa the compound of the formula in the form of a brownish yellow oil. n =l.5314. P-calc.: 11.4%. Found: 12.1%. Sca1c.: 23.6%. Found: 24.7%.

EXAMPLE 12 50 parts of the ester of the formula 8 (CHaOMl S CHzCON-CH3 are admixed with 50 parts of isooctylphenylheptaglycolether, a clear solution being obtained. An aqueous emulsion of this solution, which emulsion contains 0.02% of the ester, is sprayed on young apple trees infested with aphis. In a few hours, all aphis have been killed.

EXAMPLE 13 20 parts of the ester of the formula ll (CHaO)2P S CHQCON-CHB are admixed with 30 parts of isooctylphenyloctaglycolether and with 50 parts of a petroleum fraction which boils at 210-280", specific gravity (20) 0.92, a clear solution being obtained which is well emulsifiable in water. Such an emulsion, containing 0.05 to 0.1% of the said ester, effects a kill 011 all stages of spider mites, e.g., T etranychus telarius, Paratetranychus pilosus, etc.

EXAMPLE 14:

20 parts of the ester of the formula (CHBOMIILI) S CHgCON-CgE};

are admixed with 20 parts of laurylhexaglycolether and 60 parts of xylene, the resultant product being readily water-emulsifiable. An aqueous emulsion of this product, which emulsion contains 0.2% of the ester, is sprayed on aphis-infested potted plants (cineraria, aster, Chrysanthemum). In a short time, all aphis are dead.

EXAMPLE 15 (a) By admixing 25 parts of the ester of the formula S (01130? s CHzCON-CH3 with 25 parts of diisohexyl-heptylphenylhexaglycolether, 25 parts of xylene and 25 parts of diethyleneglycol, a product is obtained which is well emulsifiahle with water. Potted spiderwort plants of a height of about 20 cm. are each watered with 100 milliliters of an aqueous emulsion of the said product, such emulsion containing 0.02% of the active ester, care being taken that no green parts of the plant are wetted. The next day, 30 grasshopper larvae (Carausius morosus), second stage, are applied to each plant. The larvae feed on the leaves and in this way also include in their nourishment the aforesaid active ester which has been taken in by the roots of the plants and transported to the leaves. At the end of 8 days, no living larvae remain; all are dead.

(12) An aqueous emulsion of the same product, containing 0.2% of active ester, is sprayed on aphis-infected plants of Erigeron canadense, in such manner that only the bottom part of the plants (not roots) are contacted,

HO with 3 parts of tort. dodecylmercaptanundecaglycolether, 7 parts of powdered silica gel and 75 parts of kaolin. A suspension prepared from this mixture and containing 0.1% of the said ester, when sprayed on aphis, produces a complete kill in a few hours.

EXAMPLE 17 2 parts of the ester of the. formula ll (CgIIsOhP S CHzCON-CHS are admixed with 98 parts of talc, and the mixture ground in a ball mill. The product is a dusting agent which, dusted in areas infested by cockroaches (Periplaneta am'ericana), effects a 100% kill in 24 to 48 hours of all of the latter which come into contact with the dust.

Having thus disclosed the invention what is claimed is:

1. The method of combating insect and arachnid pests which comprises bringing into contact with said pests an effective quantity of a compound of the formula PSCH(iJN-R 12,0 H0 wherein each of R and R is alkyl with at most two carbon atoms, R is alkyl with at most three carbon atoms, R .is a group of the formula C H wherein n is a numeral from 0 to 3 inclusive, and Y is a chalcogen with an atomic weight from 16.00 to 32.06.

2. The method of combating insect and arachnid pests which comprises bringing into contact with the said pests an effective quantity of a compound of the formula Rio S R4 0 is H i N R. R20 1110 wherein each of R and R is alkyl with at most two carbon atoms, R is alkyl with at most three carbon atoms, R; is a group of the formula C H wherein n is a numeral from 0 to 3 inclusive.

3. The method of combating insect and arachnid pests which comprises bringing into contact with the said pests an effective quantity of a compound of the formula R30 HO wherein each of R and R is alkyl with at most two carbon atoms, R is alkyl with at most three carbon atoms, R; is a group of the formula C,,H wherein n is a numeral from 0 to 3 inclusive.

4. The method of combating insect and arachnid pests which comprises bringing an effective quantity of the compound of the formula (CHaO)zi SCH CON-CH into contact with said pests.

5. The method of combating insect and arachnid pests which comprises bringing an eifective quantity of the compound of the formula II 3 )2Ps-orno ou -01H,

CHO

into contact with said pests.

6. The method of combating insect and ar-achnid pests which comprises bringing an elfective quantity of the compound of the formula (CHsOhPS-CHgC ONCH(CH3)1 into contact with said pests.

7. The method of combating insect and arachnid pests which comprises bringing an effective quantity of the compound of the formula II z 5 )zPsoH2ooN-om CHO into contact with said pests.

8. The method of combating insect and 'arachnid pests which comprises bringing an effective quantity of the compound of the formula into contact with said pests.

9. The method of combating insect and arachnid pests which comprises bringing an eflective quantity of the compound of the formula into contact with said pests.

10. A water-emulsifiable insecticidal and acaricidal concentrate consisting essentially of a compound of the formula R20 HO wherein each of R and R is alkyl with at most two carbon atoms, R is alkyl with at most three carbon atoms, R; is a group of the formula C,,H wherein n is a numeral from 0 to 3 inclusive, and Y is a chalcogen with an atomic weight from 16.00 to 32.06, and an emulsifier therefor.

11. A Water-emulsifiable insecticidal and acaricidal concentrate consisting essentially of a compound of the formula R20 HO wherein each of R and R is alkyl with at most two carbon atoms, R is alkyl with at most three carbon atoms, R; is a group of the formula -C,,H wherein n is a numeral from O to 3 inclusive, and Y is a chalcogen with an atomic weight from 1 6.00 to 32.06, an emulsifier therefor, and a solid carrier.

12. An insecticidal and acaricidal dusting composition consisting essentially of a compound of the formula wherein each of R and R is alkyl with at most two carbon atoms, R is alkyl with at most three carbon atoms,

R is a group of the formula C H wherein n is a numeral from 0 to 3 inclusive, and Y is a chalcogen with an atomic weight from 16.00 to 32.06, and a powdered carrier therefor, said composition containing 0.005 to 0.2% by weight of said compound.

13. An insecticide-acaricide consisting essentially of an aqueous emulsion of a compound of the formula R20 GEO wherein each of R and R is alkyl with at most two carbon atoms, R is alkyl with at most three carbon atoms,

10 R is a group of the formula C I-I wherein n is a numeral from 0 to 3 inclusive, and Y is a chalcogen with an atomic weight from 16.00 to 32.06, said insecticideacaricide containing 0.005 to 0.2% by weight of said compound.

References Cited by the Examiner UNITED STATES PATENTS 2,656,360 10/53 Hagemeyer 260561 2,668,831 2/54 Tolkmith 260-461 2,712,029 6/55 Wenkle 260461 2,890,947 6/59 Annable et al. 260-461 X 2,915,429 12/59 Scherer 1-6722 2,920,993 1/60 Fairchild 167-22 2,923,738 2/60 Williams 260561 2,928,862 3/60 Willard et al. 260-461 2,955,137 10/60 Mayhew 260561 2,959,608 11/60 Crouch et a1. 260461 3,004,055 10/61 Perini et a1 260461 OTHER REFERENCES Einhorn et al.: Justus Liebigs Annalen der Chemie, vol. 343, pp. 282-284 (1905).

JULIAN S. LEVITT, Primary Examiner. 

1. THE METHOD OF COMBATING INSECT AND ARACHNID PESTS WHICH COMPRISES BRINGING INTO CONTACT WITH SAID PESTS AN EFFECTIVE QUANTITY OF A COMPOUND OF THEFORMULA 